Organic conversion with a catalyst comprising a crystalline pillared oxide material

ABSTRACT

There is provided a process for converting organic compounds using a catalyst comprising a pillared, layered crystalline oxide material. This material may be prepared by intercepting a swellable layered oxide before calcination. The intercepted material is swollen and pillared. If the material is not intercepted in this manner, it is transformed into a zeolite by calcination. The pillared material may have a large degree of catalytic activity, and it may have rather porous layers.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a division of U.S. application Ser. No. 07/811,384,filed Dec. 20, 1991, now U.S. Pat. No. 5,229,341 which is acontinuation-in-part of copending U.S. application Ser. No. 07/776,718,filed Oct. 15, 1991, now abandoned, which is a continuation of U.S.application Ser. No. 07/640,330, filed Jan. 11, 1991, now abandoned.Ser. No. 07/811,384 is also a continuation-in-part of U.S. applicationSer. Nos. 07/640,329; 07/640,339; and 07/640,341, each filed Jan. 11,1991, each now abandoned. The entire disclosures of these applicationsare expressly incorporated herein by reference.

BACKGROUND

This application relates to pillared, layered crystalline oxidematerials. These materials may be prepared by a method which preventsswellable layered intermediate structures from being transformed intonon-swellable zeolite structures.

Many layered materials are known which have three-dimensional structureswhich exhibit their strongest chemical bonding in only two dimensions.In such materials, the stronger chemical bonds are formed intwo-dimensional planes and a three-dimensional solid is formed bystacking such planes on top of each other. However, the interactionsbetween the planes are weaker than the chemical bonds holding anindividual plane together. The weaker bonds generally arise frominterlayer attractions such as Van der Waals forces, electrostaticinteractions, and hydrogen bonding. In those situations where thelayered structure has electronically neutral sheets interacting witheach other solely through Van der Waals forces, a high degree oflubricity is manifested as the planes slide across each other withoutencountering the energy barriers that arise with strong interlayerbonding. Graphite is an example of such a material. The silicate layersof a number of clay materials are held together by electrostaticattraction mediated by ions located between the layers. In addition,hydrogen bonding interactions can occur directly between complementarysites on adjacent layers, or can be mediated by interlamellar bridgingmolecules.

Laminated materials such as clays may be modified to increase theirsurface area. In particular, the distance between the layers can beincreased substantially by absorption of various swelling agents such aswater, ethylene glycol, amines, ketones, etc., which enter theinterlamellar space and push the layers apart. However, theinterlamellar spaces of such layered materials tend to collapse when themolecules occupying the space are removed by, for example, exposing theclays to high temperatures. Accordingly, such layered materials havingenhanced surface area are not suited for use in chemical processesinvolving even moderately severe conditions.

The extent of interlayer separation can be estimated by using standardtechniques such as X-ray diffraction to determine the basal spacing,also known as "repeat distance" or "d-spacing". These values indicatethe distance between, for example, the uppermost margin of one layerwith the uppermost margin of its adjoining layer. If the layer thicknessis known, the interlayer spacing can be determined by subtracting thelayer thickness from the basal spacing.

Various approaches have been taken to provide layered materials ofenhanced interlayer distance having thermal stability. Most techniquesrely upon the introduction of an inorganic "pillaring" agent between thelayers of a layered material. For example, U.S. Pat. No. 4,216,188incorporated herein by reference discloses a clay which is cross-linkedwith metal hydroxide prepared from a highly dilute colloidal solutioncontaining fully separated unit layers and a cross-linking agentcomprising a colloidal metal hydroxide solution. However, this methodrequires a highly dilute forming solution of clay (less than 1 g/l) inorder to effect full layer separation prior to incorporation of thepillaring species, as well as positively charged species of crosslinking agents. U.S. Pat. No. 4,248,739, incorporated herein byreference, relates to stable pillared interlayered clay prepared fromsmectite clays reacted with cationic metal complexes of metals such asaluminum and zirconium. The resulting products exhibit high interlayerseparation and thermal stability.

U.S. Pat. No. 4,176,090, incorporated herein by reference, discloses aclay composition interlayered with polymeric cationic hydroxy metalcomplexes of metals such as aluminum, zirconium and titanium. Interlayerdistances of up to 16A are claimed although only distances restricted toabout 9A are exemplified for calcined samples. These distances areessentially unvariable and related to the specific size of the hydroxymetal complex.

Silicon-containing materials are believed to be a highly desirablespecies of intercalating agents owing to their high thermal stabilitycharacteristics. U.S. Pat. No. 4,367,163, incorporated herein byreference, describes a clay intercalated with silica by impregnating aclay substrate with a silicon-containing reactant such as an ionicsilicon complex, e.g., silicon acetylacetonate, or a neutral speciessuch as SiCl₄. The clay may be swelled prior to or during siliconimpregnation with a suitable polar solvent such as methylene chloride,acetone, benzaldehyde, tri- or tetraalkylammonium ions, ordimethylsulfoxide. This method, however, appears to provide only amonolayer of intercalated silica resulting in a product of small spacingbetween layers, about 2-3 A as determined by X-ray diffraction.

U. S. Pat. No. 4,859,648 describes layered oxide products of highthermal stability and surface area which contain interlayered polymericoxides such as polymeric silica. These products are prepared by ionexchanging a layered metal oxide, such as layered titanium oxide, withorganic cation, to spread the layers apart. A compound such astetraethylorthosilicate, capable of forming a polymeric oxide, isthereafter introduced between the layers. The resulting product istreated to form polymeric oxide, e.g., by hydrolysis, to produce thelayered oxide product. The resulting product may be employed as acatalyst material in the conversion of hydrocarbons.

Crystalline oxides include both naturally occurring and syntheticmaterials. Examples of such materials include porous solids known aszeolites. The structures of crystalline oxide zeolites may be describedas containing corner-sharing tetrahedra having a three-dimensionalfour-connected net with T-atoms at the vertices of the net and O-atomsnear the midpoints of the connecting lines. Further characteristics ofcertain zeolites are described in Collection of Simulated XRD PowderPatterns for Zeolites by Roland yon Ballmoos, Butterworth ScientificLimited, 1984.

Synthetic zeolites are often prepared from aqueous reaction mixturescomprising sources of appropriate oxides. Organic directing agents mayalso be included in the reaction mixture for the purpose of influencingthe production of a zeolite having the desired structure. The use ofsuch directing agents is discussed in an article by Lok et al. entitled"The Role of Organic Molecules in Molecular Sieve Synthesis" appearingin Zeolites, Vol. 3, October. 1983, pp. 282-291.

After the components of the reaction mixture are properly mixed with oneanother, the reaction mixture is subjected to appropriatecrystallization conditions. Such conditions usually involve heating ofthe reaction mixture to an elevated temperature possibly with stirring.Room temperature aging of the reaction mixture is also desirable in someinstances.

After the crystallization of the reaction mixture is complete, thecrystalline product may be recovered from the remainder of the reactionmixture, especially the liquid contents thereof. Such recovery mayinvolve filtering the crystals and washing these crystals with water.However, in order to remove all of the undesired residue of the reactionmixture from the crystals, it is often necessary to subject the crystalsto a high temperature calcination e.g., at 500° C., possibly in thepresence of oxygen. Such a calcination treatment not only removes waterfrom the crystals, but this treatment also serves to decompose and/oroxidize the residue of the organic directing agent which may be occludedin the pores of the crystals, possibly occupying ion exchange sitestherein.

In accordance with aspects of inventive subject matter described herein,it has been discovered that a certain synthetic crystalline oxideundergoes a transformation during the synthesis thereof from anintermediate swellable layered state to a non-swellable final statehaving order in three dimensions, the layers being stacked upon oneanother in an orderly fashion. This transformation may occur during thedrying of the recovered crystals, even at moderate temperatures, e.g.,110° C. or greater. By interrupting the synthesis of these materialsprior to final calcination and intercepting these materials in theirswellable intermediate state, it is possible to interpose materials suchas swelling, pillaring or propping agents between these layers beforethe material is transformed into a non-swellable state. When theswollen, non-pillared form of these materials is calcined, thesematerials may be transformed into materials which have disorder in theaxis perpendicular to the planes of the layers, due to disorderedstacking of the layers upon one another.

SUMMARY

There is provided a method for preventing a layered crystalline oxidefrom being transformed by calcination into a non-swellable zeolite, saidmethod comprising the steps of:

(i) intercepting said layered crystalline oxide in an intermediate,swellable state;

(ii) swelling the swellable, layered crystalline oxide of step (i) witha swelling agent under conditions sufficient to produce a swollen,layered crystalline oxide;

(iii) pillaring the swollen, layered crystalline oxide with a pillaringagent under conditions sufficient to insert interspathic oxide materialin between the layers of the layered, crystalline oxide; and

(iv) calcining the pillared, layered crystalline oxide under conditionssufficient to transform the intercepted, layered crystalline oxide ofstep (i), in the absence of steps (ii) and (iii), into saidnon-swellable zeolite,

whereby a pillared, layered crystalline oxide is formed and thetransformation of a layered, crystalline oxide into a non-swellablezeolite is prevented.

The pillared, layered crystalline oxide, prepared by this method mayhave an Alpha Value of at least 10, e.g., 50 or greater. The individuallayers of this material may be porous, for example, having pore windowsformed by at least 8, e.g., 10, oxygen atoms. The pores in the layersmay have diameters of at least 5 Angstroms.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an X-ray diffraction pattern of an as-synthesized form of alayered material which may be swollen and pillared.

FIG. 2 is an X-ray diffraction pattern of a swollen form of the materialhaving the X-ray diffraction pattern shown in FIG. 1.

FIG. 3 is an X-ray diffraction pattern of the pillared form of thelayered material having the X-ray diffraction pattern shown in FIG. 1.

FIG. 4 is an X-ray diffraction pattern of the calcined form of theswollen material having the X-ray diffraction pattern shown in FIG. 2.

EMBODIMENTS

The present layered oxide material may be prepared from an intermediatematerial which is crystallized in the presence of, e.g., ahexamethyleneimine directing agent and which, if calcined, without beingswollen would be transformed into a material having an X-ray diffractionpattern as shown in Table 1.

                  TABLE 1                                                         ______________________________________                                        Interplanar   Relative Intensity,                                             d-Spacing (A) I/I.sub.o × 100                                           ______________________________________                                        30.0 ± 2.2 w-m                                                             22.1 ± 1.3 w                                                               12.36 ± 0.2                                                                              m-vs                                                            11.03 ± 0.2                                                                              m-s                                                             8.83 ± 0.14                                                                              m-vs                                                            6.86 ± 0.14                                                                              w-m                                                             6.18 ± 0.12                                                                              m-vs                                                            6.00 ± 0.10                                                                              w-m                                                             5.54 ± 0.10                                                                              w-m                                                             4.92 ± 0.09                                                                              w                                                               4.64 ± 0.08                                                                              w                                                               4.41 ± 0.08                                                                              w-m                                                             4.25 ± 0.08                                                                              w                                                               4.10 ± 0.07                                                                              w-s                                                             4.06 ± 0.07                                                                              w-s                                                             3.91 ± 0.07                                                                              m-vs                                                            3.75 ± 0.06                                                                              w-m                                                             3.56 ± 0.06                                                                              w-m                                                             3.42 ± 0.06                                                                              vs                                                              3.30 ± 0.05                                                                              w-m                                                             3.20 ± 0.05                                                                              w-m                                                             3.14 ± 0.05                                                                              w-m                                                             3.07 ± 0.05                                                                              w                                                               2.99 ± 0.05                                                                              w                                                               2.82 ± 0.05                                                                              w                                                               2.78 ± 0.05                                                                              w                                                               2.68 ± 0.05                                                                              w                                                               2.59 ± 0.05                                                                              w                                                               ______________________________________                                    

The values in this Table and like tables presented hereinafter weredetermined by standard techniques. The radiation was the K-alpha doubletof copper and a diffractometer equipped with a scintillation counter andan associated computer was used. The peak heights, I, and the positionsas a function of 2 theta, where theta is the Bragg angle, were determineusing algorithms on the computer associated with the diffractometer.From these, the relative intensities, 100 I/I_(o), where I_(o) is theintensity of the strongest line or peak, and d (obs.) the interplanarspacing in Angstrom Units (A), corresponding to the recorded lines, weredetermined. In Tables 1-8, the relative intensities are given in termsof the symbols w=weak, m=medium, s=strong and vs=very strong. In termsof intensities, these may be generally designated as follows:

w=0-20

m=20-40

s=40-60

vs=60-100

The material having the X-ray diffraction pattern of Table 1 is known asMCM-22 and is described in U.S. Pat. No. 4,954,325, the entiredisclosure of which is incorporated herein by reference. This materialcan be prepared from a reaction mixture containing sources of alkali oralkaline earth metal (M), e.g., sodium or potassium, cation, an oxide oftrivalent element X, e.g., aluminum, an oxide of tetravalent element Y,e.g., silicon, an organic (R) directing agent, hereinafter moreparticularly described, and water, said reaction mixture having acomposition, in terms of mole ratios of oxides, within the followingranges:

    ______________________________________                                        Reactants       Useful   Preferred                                            ______________________________________                                        YO.sub.2 /X.sub.2 O.sub.3                                                                      10-80   10-60                                                H.sub.2 O/YO.sub.2                                                                              5-100  10-50                                                OH.sup.- /YO.sub.2                                                                            0.01-1.0 0.1-0.5                                              M/YO.sub.2      0.01-2.0 0.1-1.0                                              R/YO.sub.2      0.05-1.0 0.1-0.5                                              ______________________________________                                    

In the synthesis method for preparing the material having the X-raydiffraction patter of Table 1, the source of YO₂ must be comprisedpredominately of solid Y₂, for example at least about 30 wt. % solid YO₂in order to obtain the desired crystal product. Where YO₂ is silica, theuse of a silica source containing at least about 30 wt. % solid silica,e.g., Ultrasil precipitated, spray dried silica containing about 90 wt.% silica) or HiSil (a precipitated hydrated SiO₂ containing about 87 wt.% silica, about 6 wt. % free H₂ O and about 4.5 wt. % bound H₂ O ofhydration and having a particle size of about 0.02 micron) favorscrystal formation from the above mixture and is a distinct improvementover the synthesis method taught in U.S. Pat. No. 4,439,409. If anothersource of oxide of silicon e.g., Q-Brand (a sodium silicate comprised ofabout 28.8 wt. % SiO₂, 8.9 wt. % Na₂ O and 62.3 wt. % H₂ O) is used,crystallization yields little or none of the crystalline material havingthe X-ray diffraction pattern of Table 1. Impurity phases of othercrystal structures, e.g., ZSM-12, are prepared in the lattercircumstance. Preferably, therefore, the YO₂, e.g., silica, sourcecontains at least about 30 wt. % solid YO₂, e.g., silica, and morepreferably at least about 40 wt. % solid YO₂, e.g., silica.

Crystallization of the crystalline material having the X-ray diffractionpattern of Table 1 can be carried out at either static or stirredconditions in a suitable reactor vessel, such as for example,polypropylene jars or teflon lined or stainless steel autoclaves. Thetotal useful range of temperatures for crystallization is from about 80°C. to about 225° C. for a time sufficient for crystallization to occurat the temperature used, e.g., from about 24 hours to about 60 days.Thereafter, the crystals are separated from the liquid and recovered.

The organic directing agent for use in synthesizing the presentcrystalline material from the above reaction mixture may behexamethyleneimine which has the following structural formula: ##STR1##Other organic directing agents which may be used include1,4-diazacycloheptane, azacyclooctane, aminocyclohexane,aminocycloheptane, aminocyclopentane,N,N,N-trimethyl-1-adamantanammmonium ions, andN,N,N-trimethyl-2-adamantanammmonium ions. In general, the organicdirecting agent may be selected from the group consisting ofheterocyclic imines, cycloalkyl amines and adamantane quaternaryammonium ions.

It should be realized that the reaction mixture components can besupplied by more than one source. The reaction mixture can be preparedeither batchwise or continuously. Crystal size and crystallization timeof the crystalline material will vary with the nature of the reactionmixture employed and the crystallization conditions.

Synthesis of crystals may be facilitated by the presence of at least0.01 percent, e.g., 0.10 percent or 1 percent, seed crystals (based ontotal weight) of crystalline product.

The crystalline material having the X-ray diffraction pattern of Table 1passes through an intermediate stage. The material at this intermediatestage has a different X-ray diffraction pattern than that set forth inTable 1. It has further been discovered that this intermediate materialis swellable with the use of suitable swelling agents such ascetyltrimethylammonium compounds, e.g., cetyltrimethylammoniumhydroxide. However, when this intermediate material is calcined, evenunder mild conditions, whereby the swelling agent is removed, thematerial can no longer be swollen with such swelling agent. By way ofcontrast it is noted that various layered silicates such as magadiiteand kenyaite may be swellable with cetyltrimethylammonium compounds bothprior to and after mild calcination.

The present swollen products may have relatively high interplanardistance (d-spacing), e.g., greater than about 6 Angstrom, e.g., greaterthan about 10 Angstrom and even exceeding 30 Angstrom. These swollenmaterials may be converted into pillared materials. These pillaredmaterials, particularly silica pillared materials, may be capable ofbeing exposed to severe conditions such as those encountered incalcining, e.g., at temperatures of about 450° C. for about two or morehours, e.g., four hours, in nitrogen or air, without significantdecrease, e.g., less than about 10%, in interlayer distance.

The material having the X-ray diffraction pattern of Table 1, whenintercepted in the swellable, intermediate state, prior to finalcalcination, may have the X-ray diffraction pattern shown in Table 2.

                  TABLE 2                                                         ______________________________________                                               d(A)     I/I.sub.o                                                     ______________________________________                                               13.53 ± 0.2                                                                         m-vs                                                                 12.38 ± 0.2                                                                         m-vs                                                                 11.13 ± 0.2                                                                         w-s                                                                  9.15 ± 0.15                                                                         w-s                                                                  6.89 ± 0.15                                                                         w-m                                                                  4.47 ± 0.10                                                                         w-m                                                                  3.95 ± 0.08                                                                         w-vs                                                                 3.56 ± 0.06                                                                         w-m                                                                  3.43 ± 0.06                                                                         m-vs                                                                 3.36 ± 0.05                                                                         w-s                                                           ______________________________________                                    

An X-ray diffraction pattern trace for an example of such anas-synthesized, swellable material is shown in FIG. 1. A particularexample of such an as-synthesized, swollen material is the material ofExample 1 of the aforementioned U.S. Pat. No. 4,954,325. This materialof Example 1 of U.S. Pat. No. 4,954,325 has the X-ray diffractionpattern given in the following Table 3.

                  TABLE 3                                                         ______________________________________                                        2 Theta        d(A)    I/I.sub.o × 100                                  ______________________________________                                        3.1            28.5    14                                                     3.9            22.7    <1                                                     6.53           13.53   36                                                     7.14           12.38   100                                                    7.94           11.13   34                                                     9.67           9.15    20                                                     12.85          6.89     6                                                     13.26          6.68     4                                                     14.36          6.17     2                                                     14.70          6.03     5                                                     15.85          5.59     4                                                     19.00          4.67     2                                                     19.85          4.47    22                                                     21.56          4.12    10                                                     21.94          4.05    19                                                     22.53          3.95    21                                                     23.59          3.77    13                                                     24.98          3.56    20                                                     25.98          3.43    55                                                     26.56          3.36    23                                                     29.15          3.06     4                                                     31.58          2.833    3                                                     32.34          2.768    2                                                     33.48          2.676    5                                                     34.87          2.573    1                                                     36.34          2.472    2                                                     37.18          2.418    1                                                     37.82          2.379    5                                                     ______________________________________                                    

Taking into account certain modifications, this swellable material maybe swollen and pillared by methods generally discussed in theaforementioned U.S. Pat. No. 4,859,648, the entire disclosure of whichis expressly incorporated herein be reference. The present modificationsare discussed hereinafter and include the selection of proper swellingpH and swelling agent.

Upon being swollen with a suitable swelling agent, such ascetyltrimethylammonium compound, the swollen material may have the X-raydiffraction pattern shown in Table 4.

                  TABLE 4                                                         ______________________________________                                               d(A)     I/I.sub.o                                                     ______________________________________                                               >32.2    vs                                                                   12.41 ± 0.25                                                                        w-s                                                                  3.44 ± 0.07                                                                         w-s                                                           ______________________________________                                    

The X-ray diffraction pattern of this swollen material may haveadditional lines with a d(A) spacing less than the line at 12.41 ±0.25,but none of said additional lines have an intensity greater than theline at the d(A) spacing of 12.41±0.25 or at 3.44±0.07, whichever ismore intense. More particularly, the X-ray diffraction pattern of thisswollen material may have the lines shown in the following Table 5.

                  TABLE 5                                                         ______________________________________                                               d(A)     I/I.sub.o                                                     ______________________________________                                               >32.2    vs                                                                   12.41 ± 0.25                                                                        w-s                                                                  11.04 ± 0.22                                                                        w                                                                    9.28 ± 0.19                                                                         w                                                                    6.92 ± 0.14                                                                         w                                                                    4.48 ± 0.09                                                                         w-m                                                                  3.96 ± 0.08                                                                         w-m                                                                  3.57 ± 0.07                                                                         w-m                                                                  3.44 ± 0.07                                                                         w-s                                                                  3.35 ± 0.07                                                                         w                                                             ______________________________________                                    

Even further lines may be revealed upon better resolution of the X-raydiffraction pattern. For example, the X-ray diffraction pattern may haveadditional lines at the following d(A) spacings (intensities given inparentheses): 16.7±4.0 (w-m); 6.11±0.24 (w); 4.05±0.08 (w); and3.80±0.08 (w).

In the region with d<9 A, the pattern for the swollen material isessentially like the one given in Table 2 for the unswollen material,but with the possibility of broadening of peaks.

An X-ray diffraction pattern trace for an example of such a swollenmaterial is shown in FIG. 2. The upper profile is a 10-foldmagnification of the lower profile in FIG. 2.

Upon being pillared with a suitable polymeric oxide, such as polymericsilica, the swollen material having the X-ray diffraction pattern shownin Table 4 may be converted into a material having the X-ray diffractionpattern shown in Table 6.

                  TABLE 6                                                         ______________________________________                                               d(A)     I/I.sub.o                                                     ______________________________________                                               >32.2    vs                                                                   12.38 ± 0.25                                                                        w-m                                                                  3.42 ± 0.07                                                                         w-m                                                           ______________________________________                                    

The X-ray diffraction pattern of this pillared material may haveadditional lines with a d(A) spacing less than the line at 12.38±0.25,but none of said additional lines have an intensity greater than theline at the d(A) spacing of 12.38±0.25 or 3.42±0.07, whichever is moreintense. More particularly, the X-ray diffraction pattern of thispillared material may have the lines shown in the following Table 7.

                  TABLE 7                                                         ______________________________________                                               d(A)     I/I.sub.o                                                     ______________________________________                                               >32.2    vs                                                                   12.38 ± 0.25                                                                        w-m                                                                  10.94 ± 0.22                                                                        w-m                                                                  9.01 ± 0.18                                                                         w                                                                    6.88 ± 0.14                                                                         w                                                                    6.16 ± 0.12                                                                         w-m                                                                  3.93 ± 0.08                                                                         w-m                                                                  3.55 ± 0.07                                                                         w                                                                    3.42 ± 0.07                                                                         w-m                                                                  3.33 ± 0.07                                                                         w-m                                                           ______________________________________                                    

Even further lines may be revealed upon better resolution of the X-raydiffraction pattern. For example, the X-ray diffraction pattern may haveadditional lines at the following d(A) spacings (intensities given inparentheses): 5.59±0.11 (w); 4.42±0.09 (w); 4.11±0.08 (w); 4.04±0.08(w); and 3.76±0.08 (w).

An X-ray diffraction pattern trace for an example of such a pillaredmaterial is given in FIG. 3. The upper profile is a 10-foldmagnification of the lower profile in FIG. 3.

If the material swollen with a suitable swelling agent is calcinedwithout prior pillaring another material is produced. For example, ifthe material which is swollen but not pillared is calcined in air for 6hours at 540° C., a very strong line at a d(A) spacing of greater than32.2 will no longer be observed. By way of contrast, when the swollen,pillared material is calcined in air for 6 hours at 540° C., a verystrong line at a d(A) spacing of greater than 32.2 will still beobserved, although the precise position of the line may shift.

An example of a swollen, non-pillared material, which has been calcined,has the pattern as shown in Table 8.

                  TABLE 8                                                         ______________________________________                                        2 Theta   d(A)            I/I.sub.o × 100                               ______________________________________                                        3.8       23.3            12                                                  7.02      12.59           100                                                 8.02      11.02           20                                                  9.66      9.16            14                                                  12.77     6.93            7                                                   14.34     6.18            45                                                  15.75     5.63            8                                                   18.19     4.88            3                                                   18.94     4.69            3                                                   19.92     4.46            13     broad                                        21.52     4.13            13     shoulder                                     21.94     4.05            18                                                  22.55     3.94            32                                                  23.58     3.77            16                                                  24.99     3.56            20                                                  25.94     3.43            61                                                  26.73     3.33            19                                                  31.60     2.831           3                                                   33.41     2.682           4                                                   34.62     2.591           3      broad                                        36.36     2.471           1                                                   37.81     2.379           4                                                   ______________________________________                                    

The X-ray powder pattern shown in Table 8 is similar to that shown inTable 1 except that most of the peaks in Table 8 are much broader thanthose in Table 1.

An X-ray diffraction pattern trace for an example of the calcinedmaterial corresponding to Table 8 is given in FIG. 4.

As mentioned previously, the calcined material corresponding to theX-ray diffraction pattern of Table 1 is designated MCM-22. For thepurposes of the present disclosure, the pillared material correspondingto the X-ray diffraction pattern of Table 6 is designated herein asMCM-36. The swollen material corresponding to the X-ray diffractionpattern of Table 4 is designated herein as the swollen MCM-22 precursor.The as-synthesized material corresponding to the X-ray diffractionpattern of Table 2 is referred to herein, simply, as the MCM-22precursor.

The MCM-22 precursor is one example of a layered crystalline oxide whichcan be intercepted prior to calcination and swollen and pillared(MCM-36) to prevent the transformation of the layered oxide into azeolite (MCM-22). Another example of such a layered crystalline oxide isMCM-39.

MCM-39 may be prepared from a material known as Nu-6(1). Details of thesynthesis, composition and X-ray diffraction pattern of Nu-6(1) are setforth in U.S. Pat. No. 4,397,825, the entire disclosure of which isexpressly incorporated herein by reference.

Nu-6(1) may be converted to MCM-39 by an acid treatment. MCM-39 has theX-ray diffraction pattern shown in Table 9.

                  TABLE 9                                                         ______________________________________                                               d(A)    I/I.sub.o                                                      ______________________________________                                               9.45 ± 0.18                                                                        vs                                                                    6.93 ± 0.14                                                                        w                                                                     5.28 ± 0.11                                                                        m                                                                     4.55 ± 0.09                                                                        vs                                                                    4.06 ± 0.08                                                                        s                                                                     3.70 ± 0.07                                                                        vs                                                                    3.34 ± 0.07                                                                        vs                                                                    3.29 ± 0.07                                                                        m                                                              ______________________________________                                    

Taking into account certain modifications, this swellable material maybe swollen and pillared by methods generally discussed in theaforementioned U.S. Pat. No. 4,859,648, the entire disclosure of whichis expressly incorporated herein be reference. The present modificationsare discussed hereinafter and include the selection of proper swellingpH and swelling agent.

Upon being swollen with a suitable swelling agent, such as acetyltrimethylammonium compound, the swollen MCM-39 may have the X-raydiffraction pattern shown in Table 10.

                  TABLE 10                                                        ______________________________________                                               d(A)    I/I.sub.o                                                      ______________________________________                                               >20.0   vs                                                                    6.83 ± 0.14                                                                        w                                                                     3.42 ± 0.07                                                                        w                                                              ______________________________________                                    

Upon being pillared with a suitable polymeric oxide, such as polymericsilica, the swollen MCM-39 material having the X-ray diffraction patternshown in Table 10 may be converted into a material having the X-raydiffraction pattern shown in Table 11.

                  TABLE 11                                                        ______________________________________                                               d(A)    I/I.sub.o                                                      ______________________________________                                               >20.0   vs                                                                    6.83 ± 0.14                                                                        w                                                                     3.41 ± 0.07                                                                        w                                                              ______________________________________                                    

If MCM-39 or swollen MCM-39 is calcined without prior pillaring anothermaterial designated Nu-6(2) is produced. Nu-6(2) is said to be a zeoliteand is described in the aforementioned U.S. Pat. No. 4,397,825.

Nu-6(1) may be made from an aqueous reaction mixture containing at leastone source of an oxide YO₂, e.g. silica; at least one source of an oxideX₂ O₃, e.g. alumina; and a 4,4'-bipyridyl compound. This reactionmixture may have the following molar composition:

    ______________________________________                                        YO.sub.2 X.sub.2 O.sub.3                                                                  10 to 5000  preferably 20 to 3000                                 MOH/YO.sub.2                                                                               0 to 0.1   preferably 0.01 to 0.3                                Z-/X.sub.2 O.sub.3                                                                        10 to 5000  preferably 10 to 100                                  Q/X.sub.2 O.sub.3                                                                        0.1 to 5000  preferably 1 to 500                                   H.sub.2 O/YO.sub.2                                                                        10 to 500   preferably 15 to 300                                  BOH/X.sub.2 O.sub.3                                                                        0 to 500,000                                                                             preferably 0 to 1000                                  ______________________________________                                    

where Y is silicon and/or germanium; X is one or more of aluminum,gallium, iron, chromium, vanadium, molybdenum, antimony, arsenic,manganese, or boron; M is an alkali metal or ammonium; Q is theaforesaid 4,4'-bipyridyl compound; and Z- is a strong acid radicalpresent as a salt of M and may be added as a free acid to reduce thefree OH⁻ level to a desired value. M and/or Q can be present ashydroxides or salts or inorganic or organic acids provided the MOH/YO₂requirement is fulfilled. BOH is an aliphatic or aromatic alcohol,preferably an alkanol. While not essential, an alcohol improvescrystallization in viscous reaction mixtures.

The bipyridyl may be partially or fully alkylated, e.g. methylated.

The preferred bipyridyl compound is 4,4'-bipyridyl itself.

The preferred alcohol (BOH) is methanol.

The preferred alkali metals (M) for making Nu-6(1) are sodium andpotassium.

The preferred oxide YO₂ is silica (SiO₂) and the preferred oxide X₂ O₃is alumina (Al₂ O₃).

The silica source for making Nu-6(1) can be any of those commonlyconsidered for use in synthesizing zeolites, for example powdered solidsilica, silicic acid, colloidal silica, or dissolved silica. Among thepowdered silicas usable are precipitated silicas, especially those madeby precipitation from an alkali metal silicate solution, such as thetype known as "KS 300" made by AKZO, and similar products, aerosolsilicas, fume silicas, and silica gels suitably in grades for use inreinforcing pigments for rubber or silicone rubber. Colloidal silicas ofvarious particle sizes may be used, for example 10-15 or 40-50 microns,as sold under the registered trademarks "LUDOX," "NALCOAG," and "SYTON."The usable dissolved silicas include commercially available water glasssilicates containing 0.5 to 6.0, especially 2.0 to 4.0 mols of SiO₂ permole of alkali metal oxide, "active" alkali metal silicates as definedin U.K. Pat. No. 1,193,254, and silicates made by dissolving silica inan alkali metal hydroxide or quaternary ammonium hydroxide or a mixturethereof.

The alumina source for making Nu-6(1) is most conveniently sodiumaluminate, but can be or can include aluminum, an aluminum salt of, forexample, the chloride, nitrate or sulphate, an aluminum alkoxide oralumina itself, which should preferably be in a hydrated or hydratableform such as colloidal alumina, pseudoboehmite, boshmite, gamma aluminaor the alpha or beta trihydrate.

The reaction mixture for making Nu-6(1) is reacted usually underautogeneous pressure, optionally with added gas, e.g. nitrogen, at atemperature between 85° and 250° C. until crystals of Nu-6(1) form,which can be from 1 hour to many months depending on the reactantcomposition and the operating temperature. Agitation is optional, but ispreferable since it reduces the reaction time.

At the end of the reaction, the solid phase may be collected on a filterand washed and is then ready for further steps.

Nu-6(1) may have a molar composition with ratio of X₂ O₃ :YO₂ of atleast 10. To the extent that this portion of Nu-6(1) results in negativecharges, Nu-6(1) also has cations to balance the negative charges. Moreparticularly, Nu-6(1) may have a mole ratio of 0.5 to 1.5 R₂ O:X₂ O₃,where R is a monovalent cation or 1/m of a cation of valency m. Nu-6(1)may also have water of hydration additional to water when R is H. Asindicated in the aforementioned U.S. Pat. No. 4,397,825, this additionalwater (H₂ O) may be quantified in terms of the molar ratio, X₂ O₃ :o to2000 H₂ O.

The freshly prepared Nu-6(1) may also contain nitrogen-containingcompounds well in excess of the 1.5 moles set out in the above-mentionedratio of 0.5 to 1.5 R₂ O:X₂ O₃. These nitrogen-containing compounds (Q)can be removed by thermal or oxidative degradation or by displacement bysuitably small molecules. Physically trapped nitrogen-containingcompounds do not constitute part of the R cations as discussedhereinabove. Thus, Nu-6(1) as made may have the following molarcomposition:

    0 to 1.8 M.sub.2 O:0.1 to 400 Q:X.sub.2 O.sub.3 :10 to 5000 Y.sub.2 O:0 to 2000 H.sub.2 O

wherein M is an alkali metal and/or ammonium and can include hydrogen,and M₂ O+Q is equal to or greater than 1.0.

The Nu-6(1) structure may retain from 0.1 to 0.15 moles of Q per mole ofYO₂, Q in this case being a 4,4-bipyridyl compound.

The H₂ O content of freshly prepared zeolite Nu-6(1) depends on theconditions in which it has been dried after synthesis. Indeed, if driedat temperatures at or above 200° C., it converts to zeolite Nu-6(2).

Nu-6(1) is recognizable by its X-ray diffraction pattern. As indicatedin the aforementioned U.S. Pat. No. 4,397,825, Nu-6(1) as prepared issaid to have the X-ray diffraction pattern in the following Table.

    ______________________________________                                                d(A)  I/I.sub.o                                                       ______________________________________                                                13.4  89                                                                      11.3   6                                                                      6.89   3                                                                      5.46  13                                                                      4.52  17                                                                      4.48  15                                                                      4.29  84                                                                      4.23  19                                                                      3.998 100                                                                     3.683 34                                                                      3.478 40                                                                      3.382 91                                                                      3.335 61                                                                      3.107 13                                                                      3.109 11                                                                      2.986  3                                                                      2.964  3                                                                      2.484 17                                                              ______________________________________                                    

The layers of MCM-39 may have the same molar X₂ O₃ :YO₂ ratio as theNu-6(1) from which it is prepared. More particularly, for example, thelayers of MCM-39 may have a composition involving the molarrelationship:

    X.sub.2 O.sub.3 :(n)YO.sub.2,

wherein X is a trivalent element, such as aluminum, boron, iron and/orgallium, preferably aluminum, Y is a tetravalent element such as siliconand/or germanium, preferably silicon, and n is at least about 10,usually from about 20 to about 1000, and more usually from about 20 toabout 70.

NU-6(1) may be converted to MCM-39 by an acid treatment. The acid usedto treat Nu-6(1) may be a mineral or other strong acid such ashydrochloric acid, sulfuric acid, nitric acid, or trifluoroacetic acid.The acid may be used in solution, especially in aqueous solution, havinga molar concentration of from about 0.1M to about 10M, e.g., from about0.5M to about 2.0M. The duration of contact with acid may be from about1 hour to about 48 hours. The temperature of the acid treatment may befrom ambient to about 100° C. For example, the acid treatment may takeplace at a temperature of about 90° C. Preferably, the acid treatment isrepeated one or more times under the same or different conditions inorder to more fully convert Nu-6(1) to MCM-39.

The layers of MCM-36 may have a composition involving the molarrelationship:

    X.sub.2 O.sub.3 :(n) YO.sub.2,

wherein X is a trivalent element, such as aluminum, boron, iron and/orgallium, preferably aluminum, Y is a tetravalent element such as siliconand/or germanium, preferably silicon, and n is at least about 5, usuallyfrom about 10 to about 150, more usually from about 10 to about 60, andeven more usually from about 10 to about 40.

To the extent that the layers of MCM-36 and MCM-39 have negativecharges, these negative charges are balanced with cations. For example,expressed in terms of moles of oxides, the layers of MCM-36 and MCM-39may have a ratio of 0.5 to 1.5 R₂ O:X₂ O₃, where R is a monovalentcation or 1/m of a cation of valency m.

The pillared material of the present disclosure adsorbs significantamounts of commonly used test adsorbate materials, i.e., cyclohexane,n-hexane and water. Adsorption capacities for MCM-36, especially thesilica pillared material, of the present invention may range at roomtemperature as follows:

    ______________________________________                                        Adsorbate    Capacity, Wt. Percent                                            ______________________________________                                        n-hexane     17-40                                                            cyclohexane  17-40                                                            water        10-40                                                            ______________________________________                                    

wherein cyclohexane and n-hexane sorption are measured at 20 Torr andwater sorption is measured at 12 Torr. Adsorption capacities for thepillared MCM-39, especially silica pillared MCM-39, may range at roomtemperature as follows:

    ______________________________________                                        Adsorbate    Capacity, Wt. Percent                                            ______________________________________                                        n-hexane     10-40                                                            cyclohexane  10-40                                                            water        10-40                                                            ______________________________________                                    

wherein cyclohexane and n-hexane sorption are measured at 20 Torr andwater sorption is measured at 12 Torr.

The swellable material, used to form the swollen material of the presentdisclosure, may be initially treated with a swelling agent. Suchswelling agents are materials which cause the swellable layers toseparate by becoming incorporated into the interspathic region of theselayers. The swelling agents are removable by calcination, preferably inan oxidizing atmosphere, whereby the swelling agent becomes decomposedand/or oxidized.

Suitable swelling agents may comprise a source of organic cation, suchas quaternary organoammonium or organophosphonium cations, in order toeffect an exchange of interspathic cations. Organoammonium cations, suchas n-octylammonium, showed smaller swelling efficiency than, forexample, cetyltrimethylammonium. A pH range of 11 to 14 for MCM-22precursor, 10 to 14 for MCM-39, preferably 12.5 to 13.5 for both MCM-22precursor and MCM-39, is generally employed during treatment with theswelling agent.

The swellable material is preferably not dried prior to being swollen.This swellable material may be in the form of a wet cake having a solidscontent of less than 30% by weight, e.g., 25 wt % or less.

The foregoing swelling treatment results in the formation of a layeredoxide of enhanced interlayer separation depending upon the size of theorganic cation introduced. In one embodiment, a series of organic cationexchanges can be carried out. For example, an organic cation may beexchanged with an organic cation of greater size, thus increasing theinterlayer separation in a step-wise fashion. When contact of thelayered oxide with the swelling agent is conducted in aqueous medium,water is trapped between the layers of the swollen species.

The organic-swollen species may be treated with a compound capable ofconversion, e.g., by hydrolysis and/or calcination, to pillars of anoxide, preferably to a polymeric oxide. Where the treatment involveshydrolysis, this treatment may be carried out using the water alreadypresent in organic-swollen material. In this case, the extent ofhydrolysis may be modified by varying the extent to which theorganic-swollen species is dried prior to addition of the polymericoxide precursor.

It is preferred that the organic cation deposited between the layers becapable of being removed from the pillared material without substantialdisturbance or removal of the interspathic polymeric oxide. For example,organic cations such as cetyltrimethylammonium may be removed byexposure to elevated temperatures, e.g., calcination, in nitrogen orair, or by chemical oxidation preferably after the interspathicpolymeric oxide precursor has been converted to the polymeric oxidepillar in order to form the pillared layered product.

These pillared layered products, especially when calcined, exhibit highsurface area, e.g., greater than 300 m² /g, and thermal and hydrothermalstability making them highly useful as catalysts or catalytic supports,for hydrocarbon conversion processes, for example, alkylation.

Insertion of the organic cation between the adjoining layer serves tophysically separate the layers in such a way as to make the layeredmaterial receptive to the interlayer addition of a polymeric oxideprecursor. In particular, cetyltrimethylammonium cations have been founduseful. These cations are readily incorporated within the interlayerspaces of the layered oxide serving to prop open the layers in such away as to allow incorporation of the polymeric oxide precursor. Theextent of the interlayer spacing can be controlled by the size of theorganoammonium ion employed.

Interspathic oxide pillars, which may be formed between the layers ofthe propped or swollen oxide material, may include an oxide, preferablya polymeric oxide, of zirconium or titanium or more preferably of anelement selected from Group IVB of the Periodic Table (FischerScientific Company Cat. No. 5-702-10, 1978), other than carbon, i.e.,silicon, germanium, tin and lead. Other suitable oxides include those ofGroup VA, e.g., V, Nb, and Ta, those of Group IIA, e.g., Mg or those ofGroup IIIB, e.g., Most preferably, the pillars include polymeric silica.In addition, the oxide pillars may include an element which providecatalytically active acid sites in the pillars, preferably aluminum.

The oxide pillars are formed from a precursor material which may beintroduced between the layers of the organic "propped" species as anionic or electrically neutral compound of the desired elements, e.g.,those of Group IVB. The precursor material may be an organometalliccompound which is a liquid under ambient conditions. In particular,hydrolyzable compounds, e.g., alkoxides, of the desired elements of thepillars may be utilized as the precursors. Suitable polymeric silicaprecursor materials include tetraalkylsilicates, e.g.,tetrapropylorthosilicate, tetramethylorthosilicate and, most preferably,tetraethylorthosilicate. Suitable polymeric silica precursor materialsalso include quaternary ammonium silicates, e.g., tetramethylammoniumsilicate (i.e. TMA silicate). Where the pillars also include polymericalumina, a hydrolyzable aluminum compound can be contacted with theorganic "propped" species before, after or simultaneously with thecontacting of the propped layered oxide with the silicon compound.Preferably, the hydrolyzable aluminum compound employed is an aluminumalkoxide, e.g., aluminum isopropoxide. If the pillars are to includetitania, a hydrolyzable titanium compound such as titanium alkoxide,e.g., titanium isopropoxide, may be used.

After calcination to remove the organic propping agent, the finalpillared product may contain residual exchangeable cations. Suchresidual cations in the layered material can be ion exchanged by knownmethods with other cationic species to provide or alter the catalyticactivity of the pillared product. Suitable replacement cations includecesium, cerium, cobalt, nickel, copper, zinc, manganese, platinum,lanthanum, aluminum, ammonium, hydronium and mixtures thereof.

Particular procedures for intercalating layered materials with metaloxide pillars are described in U.S. Pat. Nos. 4,831,005; 4,831,006; and4,929,587. The entire disclosures of these patents are expresslyincorporated herein by reference. U.S. Pat. No. 4,831,005 describesplural treatments with the pillar precursor. U.S. Pat. No. 4,929,587describes the use of an inert atmosphere, such as nitrogen, to minimizethe formation of extralaminar polymeric oxide during the contact withthe pillar precursor. U.S. Pat. No. 4,831,006 describes the use ofelevated temperatures during the formation of the pillar precursor.

The resulting pillared products may exhibit thermal stability attemperatures of 450° C. or even higher as well as substantial sorptioncapacities. The pillared products may possess a basal spacing of atleast about 20 A, e.g., at least about 32.2 A and surface areas greaterthan 300 m² /g.

The pillared, layered materials described herein can optionally be usedin intimate combination with a hydrogenating component such as tungsten,vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or anoble metal such as platinum or palladium where ahydrogenation-dehydrogenation function is to be performed. Suchcomponent can be exchanged into the composition, impregnated therein orintimately physically admixed therewith. Such component can beimpregnated in, or on, the layered material such as, for example, by, inthe case of platinum, treating the layered material with a solutioncontaining a platinum metal-containing ion. Thus, suitable platinumcompounds for this purpose include chloroplatinic acid, platinouschloride and various compounds containing the platinum amine complex.

The pillared, layered material may be subjected to thermal treatment,e.g., to decompose organoammonium ions. This thermal treatment isgenerally performed by heating one of these forms at a temperature of atleast about 370° C. for at least 1 minute and generally not longer than20 hours. While subatmospheric pressure can be employed for the thermaltreatment, atmospheric pressure is preferred simply for reasons ofconvenience.

The swollen materials of the present disclosure are useful asintermediates for preparing the pillared and calcined, swollen materialsdescribed herein with particular reference to Table 4 (pillaredmaterial) and Table 5 (calcined, swollen material). The present pillaredmaterials are useful as catalysts, catalyst supports and sorbents.

Prior to its use in catalytic processes described herein, the pillared,layered material catalyst is preferably dehydrated, at least partially.This dehydration can be done by heating the crystals to a temperature inthe range of from about 200° C. to about 595° C. in an atmosphere suchas air, nitrogen, etc., and at atmospheric, subatmospheric orsuperatmospheric pressures for between about 30 minutes to about 48hours. Dehydration can also be performed at room temperature merely byplacing the Dillared, layered material in a vacuum, but a longer time isrequired to obtain a sufficient amount of dehydration.

The pillared, layered material catalyst can be shaded into a widevariety of particle sizes. Generally speaking, the particles can be inthe form of a powder, a granule, or a molded product such as anextrudate having a particle size sufficient to pass through a 2 mesh(Tyler) screen and be retained on a 400 mesh (Tyler) screen. In caseswhere the catalyst is molded, such as by extrusion, the pillared,layered material can be extruded before drying or partially dried andthen extruded.

It may be desired to incorporate the pillared, layered material withanother material which is resistant to the temperatures and otherconditions employed in the catalytic processes described herein. Suchmaterials include active and inactive materials and synthetic ornaturally occurring zeolites as well as inorganic materials such asclays, silica and/or met oxides such as alumina. The latter may beeither naturally occurring or in the form of gelatinous precipitates orgels including mixtures of silica and metal oxides. Use of a material inconjunction with pillared, layered material, i.e., combined therewith orpresent during its synthesis, which itself is catalytically active maychange the conversion and/or selectivity of the catalyst. Inactivematerials suitably serve as diluents to control the amount of conversionso that products can be obtained economically and orderly withoutemploying other means for controlling the rate of reaction. Thesematerials may be incorporated into naturally occurring clays, e.g.,bentonite and kaolin, to improve the crush strength of the catalystunder commercial operating conditions. Said materials, i.e., clays,oxides, etc., function as binders for the catalyst. It is desirable toprovide a catalyst having good crush strength because in commercial use,it is desirable to prevent the catalyst from breaking down intopowder-like materials. These clay binders have been employed normallyonly for the purpose of improving the crush strength of the catalyst.

Naturally occurring clays which can be composited with pillared, layeredmaterials include the montmorillonite and kaolin family, which familiesinclude the subbentonites, and the kaolins commonly known as Dixie,McNamee, Georgia and Florida clays or others in which the main mineralconstituent is halloysite, kaolinite, dickite, nacrite, or anauxite.Such clays can be used in the raw state as originally mined or initiallysubjected to calcination, acid treatment or chemical modification.Binders useful for compositing with layered materials also includeinorganic oxides, notably alumina.

In addition to the foregoing materials, the pillared, layered materialscan be composited with a porous matrix material such as silica-alumina,silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia,silica-titania as well as ternary compositions such assilica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesiaand silica-magnesia-zirconia.

The relative proportions of finely divided pillared, layered materialsand inorganic oxide matrix vary widely, with the pillared, layeredmaterial content ranging from about 1 to about 90 percent by weight andmore usually, particularly when the composite is prepared in the form ofbeads, in the range of about 2 to about 80 weight of the composite.

The pillared, layered material of the present invention, particularlyMCM-36, especially silica pillared MCM-36, is useful as a catalystcomponent for a variety of organic, e.g., hydrocarbon, compoundconversion processes. Such conversion processes include, as non-limitingexamples, cracking hydrocarbons with reaction conditions including atemperature of from about 300° C. to about 700° C., a pressure of fromabout 0.1 atmosphere (bar) to about 30 atmospheres and a weight hourlyspace velocity of from about 0.1 to about 20; dehydrogenatinghydrocarbon compounds with reaction conditions including a temperatureof from about 300° C. to about 700° C., a pressure of from about 0.1atmosphere to about 10 atmospheres and a weight hourly space velocity offrom about 0.1 to about 20; converting paraffins to aromatics withreaction conditions including a temperature of from about 100° C. toabout 700° C., a pressure of from about 0.1 atmosphere to about 60atmospheres, a weight hourly space velocity of from about 0.5 to about400 and a hydrogen/hydrocarbon mole ratio of from about 0 to about 20;converting olefins to aromatics, e.g. benzene, toluene and xylenes, withreaction conditions including a temperature of from about 100° C. toabout 700° C., a pressure of from about 0.1 atmosphere to about 60atmospheres, a weight hourly space velocity of from about 0.5 to about400 and a hydrogen/hydrocarbon mole ratio of from about 0 to about 20;converting alcohols, ,e.g. methanol, or ethers, e.g. dimethylether, ormixtures thereof to hydrocarbons including aromatics with reactionconditions including a temperature of from about 300° C. to about 550°C., more preferably from about 370° C. to about 500° C., a pressure offrom about 0.01 psi to about 2000 psi, more preferably from about 0.1psi to about 500 psi, and a liquid hourly space velocity of from about0.5 to about 100: isomerizing xylene feedstock components with reactionconditions including a temperature of from about 230° C. to about 510°C., a pressure of from about 3 atmospheres to about 35 atmospheres, aweight hourly space velocity of from about 0.1 to about 200 and ahydrogen/hydrocarbon mole ratio of from about 0 to about 100;disproportionating toluene with reaction conditions including atemperature of from about 200° C. to about 760° C. a pressure of fromabout atmospheric to about 60 atmospheres and a weight hourly spacevelocity of from about 0.08 to about 20; alkylating isoalkanes, e.g.isobutane, with olefins, e.g. 2-butene, with reaction conditionsincluding a temperature of from about -25° C. to about 400° C., e.g.from about 75° C. to about 200° C., a pressure of from below atmosphericto about 5000 psig, e.g. from about atmospheric to about 1000 psig, aweight hourly space velocity based on olefin of from about 0.01 to about100, e.g. from about 0.1 to about 20, and a mole ratio of totalisoalkane to total olefin of from about 1:2 to about 100:1, e.g. fromabout 3:1 to about 30:1; alkylating aromatic hydrocarbons, e.g. benzeneand alkylbenzenes, in the presence of an alkylating agent, e.g.,olefins, formaldehyde, alkyl halides and alcohols, with reactionconditions including a temperature of from about 340° C. to about 500°C., a pressure of from about atmospheric to about 200 atmospheres, aweight hourly space velocity of from about 2 to about 2000 and anaromatic hydrocarbon/alkylating agent mole ratio of from about 1/1 toabout 20/1; and transalkylating aromatic hydrocarbons in the presence ofpolyalkylaromatic hydrocarbons with reaction conditions including atemperature of from about 340° C. to about 500° C., a pressure of fromabout atmospheric to about 200 atmospheres, a weight hourly spacevelocity of from about 10 to about 1000 and an aromatichydrocarbon/polyalkylaromatic hydrocarbon mole ratio of from about 1/1to about 16/1.

Alpha Values are reported herein for various materials. It is noted thatthe Alpha Value is an approximate indication of the catalytic crackingactivity of the catalyst compared to a standard catalyst and it givesthe relative rate constant (rate of normal hexane conversion per volumeof catalyst per unit time). It is based on the activity of the highlyactive silica-alumina cracking catalyst taken as an Alpha of 1 (RateConstant=0.016 sec⁻¹ ). The Alpha Test is described in U.S. Pat. No.3,354,078, in the Journal of Catalysis, Vol. 4, p. 527 (1965); Vol. 6,p. 278 (1966); and Vol. 61, p. 395 (1980), each incorporated herein byreference as to that description. The experimental conditions of thetest preferably include a constant temperature of 538° C. and a variableflow rate as described in detail in the Journal of Catalysis, Vol. 61,p. 395.

MCM-36, especially when the layers thereof are composed of analuminosilicate, may be a very catalytically active material. By way ofcontrast, other layered materials, such as clays, magadiite, kenyaits,and titanares, in pillared form are much less catalytically active thanthe very catalytically active forms of the pillared layered oxide,MCM-36. One measure of the catalytic activity of MCM-36 is the AlphaValue for MCM-36. Various catalytically active forms of MCM-36 may haveAlpha Values in excess of 10, e.g., 50 or greater. Particularlycatalytically active forms of MCM-36 comprise those with aluminosilicatelayers, these layers having a silica to alumina molar ratio of 300 orless.

Another distinguishing feature of MCM-36, relative to other pillaredlayered oxides, is the porosity of the layers of MCM-36. Although otherpillared oxide materials, such as pillared clays and the pillaredmaterials, e.g., pillared silicates and titanates, discussed in theaforementioned U.S. Pat. No. 4,859,648, have considerable porosity as aresult of open interspathic regions, the individual layers of thesematerials are relatively dense, lacking pore windows formed by 8 or moreoxygen atoms. On the other hand, the layers of MCM-36 would appear tohave continuous channels having pore windows formed by rings of at least8 oxygen atoms. More particularly, these pore windows in the layers ofMCM-36 would appear to be formed by rings of 10 oxygen atoms. Asindicated by argon physisorption measurements, the channels in thelayers of MCM-36 have an effective pore diameter of greater than about 5Angstroms.

Various crystallites from the Examples which follow were examined bytransition electron microscopy (TEM).

EXAMPLE 1

This Example describes the synthesis of a material which may be swollenand pillared. Water, sodium hydroxide, sodium aluminate, silica(Ultrasil), and hexamethyleneimine (HMI) were combined in the followingratios:

    2.5 Na.sub.2 O:Al.sub.2 O.sub.3 :30SiO.sub.2 :10HMI:580H.sub.2 O.

The reaction mixture was heated in an autoclave to 143° C. for 96 hours.The X-ray diffraction pattern for this material is shown pictorially inFIG. 1.

EXAMPLE 2

A mixture of a 29% solution of cetyltrimethylammonium(N,N,N-trimethyl-1-hexadecanaminium) hydroxide, 40% tetrapropylammoniumhydroxide and wet cake of Example 1 (20% solids) in the relative weightratio 105:33:27, respectively, was heated in an autoclave at 105° C.with stirring for 42 hours. The solid product was isolated bydecantation and filtration, and the wet cake was washed twice by mixingwith water and filtration. The swollen material had the X-raydiffraction pattern given in the following Table 12.

                  TABLE 12                                                        ______________________________________                                        2 Theta        d(A)   I/I.sub.o × 100                                   ______________________________________                                        1.6            55.2   100                                                     4.88           18.1   2                                                       6.38           13.85  3                                                       7.15           12.36  21                                                      7.96           11.11  6                                                       9.47           9.34   4                                                       12.81          6.91   2                                                       14.56          6.08   1                                                       19.99          4.44   9                                                       21.44          4.14   5                                                       21.88          4.06   7                                                       22.44          3.96   8                                                       23.35          3.81   3                                                       24.91          3.57   6                                                       25.90          3.44   21                                                      26.53          3.36   4                                                       ______________________________________                                    

EXAMPLE 3

The product of Example 2 (24% solids) was combined with a 10% solutionof silica in aqueous tetramethylammonium hydroxide (molar ratio TMA:SiO₂=0.5) in a weight ratio 1:15. The mixture was heated for 20 hr in thesteambox, filtered and air dried, The solid was contacted three timeswith 1M ammonium nitrate (10 ml per 1 ml of solid) and the final productwas obtained upon calcination at 540° C. The pillared, calcined materialhad the X-ray difraction pattern given in the following Table 13.

                  TABLE 13                                                        ______________________________________                                        2 Theta        d(A)   I/I.sub.o × 100                                   ______________________________________                                        1.9            46.5   100                                                     7.17           12.33  9.0                                                     8.13           10.87  3.1                                                     9.88           8.95   1.4                                                     12.90          6.86   0.9                                                     14.41          6.15   3.7                                                     16.01          5.54   0.9                                                     20.16          4.40   1.5                                                     21.12          4.21   0.9                                                     21.65          4.10   1.4                                                     22.03          4.03   2.2                                                     22.67          3.92   3.1                                                     23.78          3.74   1.8                                                     25.10          3.55   2.2                                                     26.08          3.42   7.8                                                     26.84          3.32   2.2                                                     ______________________________________                                    

EXAMPLE 4

In this case the swelling reagent was prepared by contacting a 29%solution of cetyltrimethylammononium(N,N,N-trimethyl-1-hexadecanaminium) chloride with ahydroxide-for-halide exchange resin (one liter of wet resin with 1.4milliequivalent/ml exchange capacity per 3 l of the solution). It willbe referred to as 29% CTMA-OH.

A mixture of 30 g of the Example 1 wet cake (30% solids) and 150 g ofthe 29% CTMA-OH solution was reacted in the steambox for 65 hours. Theproduct was isolated by filtration, washed twice with 50 ml of water andair dried overnight yielding 10.6 g of the swollen product. The X-raydiffraction pattern for this swollen material is shown pictorially inFIG. 2. The X-ray diffraction pattern for this swollen material is alsogiven in the following Table 14.

                  TABLE 14                                                        ______________________________________                                        2 Theta   d(A)         I/I.sub.o × 100                                  ______________________________________                                        1.7       52.0         100                                                    2.8       31.6         20                                                     5.24      16.86        10                                                     5.61      15.75        6                                                      7.13      12.40        32                                                     7.99      11.06        5                                                      9.58      9.23         3                                                      12.81     6.91         3                                                      13.98     6.33         1      broad                                           14.60     6.07         2                                                      15.69     5.65         2                                                      19.60     4.53         11     broad                                           21.29     4.17         12                                                     21.92     4.05         6                                                      22.44     3.96         10                                                     23.27     3.82         6      broad shoulder                                  24.94     3.57         9                                                      25.93     3.44         26                                                     26.60     3.35         8                                                      28.00     3.19         3      broad                                           29.08     3.07         1                                                      31.51     2.839        2                                                      33.09     2.707        1      broad                                           33.75     2.656        1      broad                                           34.70     2.585        1      broad                                           36.30     2.475        1                                                      37.09     2.424        1                                                      37.74     2.384        3                                                      ______________________________________                                    

EXAMPLE 5

This Example describes the pillaring of the swollen material of Example4. The swollen material (8.6 g) was slurried with 50 g oftetraethylorthosilicate (TEOS) and heated at 80° C. for 24 hours underthe stream of nitrogen. After filtration and overnight drying theproduct (7.15 g) was hydrolyzed in water for 5 hr giving the pillaredmaterial (6.6 g) containing 68% solids based upon calcination at 450° C.The X-ray diffraction pattern for this pillared material is shownpictorially in FIG. 3. TEM analysis of crystallites confirmed that thelayers remained separated after this pillaring procedure. The X-raydiffraction pattern for this pillared, calcined material is also givenin the following Table 15.

                  TABLE 15                                                        ______________________________________                                        2 Theta        d(A)    I/I.sub.o × 100                                  ______________________________________                                        1.7            52.0    100                                                    7.14           12.38   43.9                                                   8.02           11.02   14.3                                                   9.75           9.07    7.2                                                    12.82          6.90    2.8                                                    14.36          6.17    18.9                                                   15.95          5.56    1.7                                                    20.01          4.44    7.0                                                    21.57          4.12    6.1                                                    21.99          4.04    9.1                                                    22.58          3.94    13.9                                                   23.65          3.76    8.7                                                    25.04          3.56    11.1                                                   26.02          3.42    35.4                                                   26.71          3.34    10.2                                                   31.62          2.829   2.2                                                    33.44          2.680   2.0                                                    36.42          2.467   1.1                                                    37.15          2.420   0.4                                                    37.87          2.376   2.2                                                    ______________________________________                                    

EXAMPLE 6

This Example describes another embodiment of swelling the material ofExample 1 using a different swelling medium. The swelling reagent, wasprepared by contacting a solution of cetyltrimethylammonium(N,N,N-trimethyl-1-hexadecanaminium) chloride composed of 50% of thelatter, 35% 2-propanol and 15% water, with a hydroxide-for-halideexchange resin (two exchanges using 1/2 liter of wet: resin with 1.4milliequivalent/ml exchange capacity per 1 l of the solution; 200 ml ofethanol was also added). It will be referred to as 50% CTMA-OH.

300 ml of the slurry containing about 20% of the material of Example 1was mixed with 300 ml of the 50% CTMA-OH solution. The mixture washeated in a 1 l autoclave for 24 hours at 150° C. with stirring. Theproduct was isolated by filtration, washed twice with 400 ml of waterand air dried overnight yielding about 140 g of the swollen product. TheX-ray diffraction pattern for this swollen material is given in thefollowing Table 16.

                  TABLE 16                                                        ______________________________________                                        2 Theta   d(A)         I/I.sub.o × 100                                  ______________________________________                                        1.8       49.1         100                                                    5.18      17.06        25                                                     7.20      12.28        55                                                     8.09      10.93        9                                                      9.60      9.21         7                                                      12.87     6.88         4                                                      14.67     6.04         3                                                      15.80     5.61         2                                                      19.73     4.50         22     broad                                           21.45     4.14         18                                                     22.00     4.04         5                                                      22.52     3.95         22                                                     23.39     3.80         9      broad shoulder                                  25.03     3.56         19                                                     26.02     3.42         59                                                     26.69     3.34         16                                                     29.19     3.06         3                                                      31.60     2.831        3                                                      33.16     2.702        2                                                      36.37     2.470        2                                                      37.02     2.428        1                                                      37.82     2.379        7                                                      ______________________________________                                    

EXAMPLE 7

This Example describes swelling of the material prepared from thesynthesis mixture of Example 1 that has been crystallized for 48 hours(see below) rather than 96 hours.

The combination of 504 g of water, 11.4 g of 50% sodium hydroxide, 11.4g of sodium aluminate (43.5% Al₂ O₃, 30% Na₂ O), 64.9 g of silica(Ultrasil) and 34.2 g of hexamethyleneimine was reacted in an autoclaveat 143° C. for 48 hours with stirring. The product was filtered andwashed thoroughly with water.

500 g of the wet cake material (24% solids) described above was mixedwith 3 l of 29% CTMA-OH solution and stirred for 48 hours at roomtemperature. The swollen product was isolated by filtration, washedtwice with 500 ml of water and air dried overnight. The X-raydiffraction pattern for this swollen material is given in the followingTable 17.

                  TABLE 17                                                        ______________________________________                                        2 Theta   d(A)         I/I.sub.o × 100                                  ______________________________________                                        1.7       52.0         100                                                    5.18      17.06        7.3                                                    6.81      12.98        2.3                                                    7.10      12.45        5.7                                                    8.79      10.06        2.7    very broad                                      12.73     6.95         0.6                                                    13.82     6.41         0.4                                                    14.55     6.09         0.3                                                    15.59     5.68         0.7                                                    18.39     4.82         1.3    broad shoulder                                  19.06     4.66         2.6    shoulder                                        19.77     4.49         4.8                                                    21.01     4.23         3.4    broad                                           22.28     3.99         5.0                                                    23.35     3.81         2.3    broad shoulder                                  24.91     3.57         3.0                                                    25.90     3.44         8.0                                                    26.50     3.36         4.4                                                    ______________________________________                                    

EXAMPLE 8

This Example describes pillaring of the swollen material of Example 7.235 g of the product was ground and combined with 1.4 liter of TEOS andtreated by a procedure similar to Example 5. The product contained 65%solids based on calcination at 540° C. A sample of the calcined productwas examined by argon physisorption which revealed a dual pore systemwith diameters of 6.3 Angstroms and about 28 Angstroms.

To determine the pore diameters, a 0.2 gram sample of the product ofExample 8 was placed in a glass sample tube and attached to aphysisorption apparatus as described in U.S. Pat. No. 4,762,010.

The sample was heated to 300° C. for 3 hours in vacuo to remove adsorbedwater. Thereafter, the sample was cooled to 87° K. by immersion of thesample tube in liquid argon. Metered amounts of gaseous argon were thenadmitted to the sample in stepwise manner as described in U.S. Pat. No.4,762,010, column 20. From the amount of argon admitted to the sampleand the amount of argon left in the gas space above the sample, theamount of argon adsorbed can be calculated. For this calculation, theideal gas law and the calibrated sample volumes were used. (See also S.J. Gregg et al., Adsorption, Surface Area and Porosity, 2nd ed.,Academic Press, 1982). In each instance, a graph of the amount adsorbedversus the relative pressure above the sample, at equilibrium,constitutes the adsorption isotherm. It is common to use relativepressures which are obtained by foxing the ratio of the equilibriumpressure and the vapor pressure P_(o) of the adsorbate at thetemperature where the isotherm is measured. Sufficiently small amountsof argon were admitted in each step to generate 168 data points in therelative pressure range from 0 to 0.6. At least about 100 points arerequired to define the isotherm with sufficient detail.

The step (inflection) in the isotherm, indicates filling of a poresystem. The size of the step indicates the amount adsorbed, whereas theposition of the step in terms of P/P_(o) reflects the size of the poresin which the adsorption takes place. Larger pores are filled at higherP/P_(o). In order to better locate the position of the step in theisotherm, the derivative with respect to log (P/P_(o)) is formed. Theadsorption peak (stated in terms of log (P/P_(o))) may be related to thephysical pore diameter (Å) by the following formula: ##EQU1## whered=pore diameter in nanometers, K=32.17, S=0.2446, L=d+0.19, and D=0.57.

This formula is derived from the method of Horvath and Kawazoe (G.Horvath et al., J. Chem. Eng. Japan, 16 (6) 470(1983)). The constantsrequired for the implementation of this formula were determined from ameasured isotherm of AlPO₄ -5 and its known pore size. This method isparticularly useful for microporous materials having pores of up toabout 60 Angstroms in diameter.

The X-ray diffraction pattern for this pillared, calcined material ofExample 8 is given in the following Table 18.

                  TABLE 18                                                        ______________________________________                                        2 Theta    d(A)           I/I.sub.o × 100                               ______________________________________                                        1.7        52.0           100                                                 7.13       12.40          23.3                                                8.08       10.94          7.3    broad                                        12.84      6.89           1.5                                                 14.38      6.16           8.4                                                 15.83      5.60           0.9                                                 19.88      4.47           2.3    broad                                        21.61      4.11           2.2                                                 22.07      4.03           3.3    broad                                        22.67      3.92           4.3    broad                                        23.67      3.76           2.7                                                 25.06      3.55           4.0                                                 26.06      3.42           12.8                                                26.75      3.33           4.1                                                 ______________________________________                                    

EXAMPLE 9

This Example describes a preparation involving pillaring with an aqueoussolution of tetramethylammnomium silicate, TMA-Si, previously defined inExample 3 and formulation of the alumina bound catalyst.

The swollen product was obtained by reacting 330 g of the Example 1 wetcake (42% solids) and 2700 ml of 29% CTMA-OH for 48 hours in thesteambox. The solid was isolated by filtration, washed by contactingwith 0.5 l of water and air dried. The X-ray diffraction pattern of thisswollen material is given in the following Table 19.

                  TABLE 19                                                        ______________________________________                                        2 Theta    d(A)           I/I.sub.o × 100                               ______________________________________                                        1.7        52.0           100                                                 2.7        32.7           28.1                                                5.38       16.43          10.8                                                7.12       12.41          14.5                                                8.10       10.91          2.9                                                 9.61       9.20           1.5    broad                                        12.77      6.93           1.0                                                 14.50      6.11           0.9                                                 19.88      4.47           6.8    broad                                        21.41      4.15           6.6                                                 21.94      4.05           4.4                                                 22.46      3.96           7.7                                                 23.05      3.86           3.3    shoulder                                     23.60      3.77           3.2    shoulder                                     24.93      3.57           4.8                                                 25.93      3.44           12.4                                                26.55      3.36           4.7    broad                                        ______________________________________                                    

25 g of the above swollen material was slurried with 150 g of the TMA-Sisolution and heated in a steambox for 20 hours. The solid product wasfiltered and air dried (yield 31 g). A small sample was calcined toverify that it was the pillaring was successful.

The remainder of the product was mixed with alumina alpha-monohydrate(Kaiser alumina) (solid ratio 65:35) and ion exchanged by contactingthree times with 1M ammonium nitrate. After drying, the solid waspelletized and was calcined by a hybrid method: 3 hr in nitrogen at 450°C. followed by slow bleeding of air and full air calcination at 540° C.for 6 hours.

EXAMPLE 10

This Example describes the preparation, swelling and pillaring of thematerial related to that of Example 1 but with a higher content ofalumina (Si/Al₂ ratio around 18).

A combination of 258 g of water, 6 g of 50% sodium hydroxide, 13.4 g ofsodium aluminate (25% Al₂ O₃, 19% Na₂ O), 51.4 g of silica (Ultrasil),and 27.1 g of hexamethyleneimmine was reacted in an autoclave at 143° C.for 34 hours with stirring. The solid product was isolated by filtrationand washed with water.

70 g of the above wet cake (about 20% solids) was swollen by contactingwith 300 ml of 29% CTMA-OH for 43 hours at room temperature withstirring. The product was isolated by filtration, washed with water andair dried. It was then pillared (19 g) by mixing with TMA-Si (113 g) andheating in the steambox for 20 hr. Further processing, including bindingwith alumina, exchange and calcination was carried out as in Example 9.The X-ray diffraction pattern for this pillared, calcined material isgiven in the following Table 20.

                  TABLE 20                                                        ______________________________________                                        2 Theta   d(A)         I/I.sub.o × 100                                  ______________________________________                                        1.5       58.9         100                                                    7.13      12.40        55                                                     8.20      10.78        19     broad                                           12.84     6.89         5                                                      14.41     6.15         26                                                     15.56     5.69         5                                                      20.04     4.43         9                                                      21.70     4.10         9      broad shoulder                                  22.14     4.01         12     broad                                           22.60     3.93         19     broad                                           23.50     3.79         13     broad                                           25.09     3.55         11                                                     26.04     3.42         33                                                     26.64     3.35         21                                                     ______________________________________                                    

EXAMPLE 11

This Example describes swelling of the material of Example 1 withdodecyltrimethylammonium chloride/hydroxide.

The swelling reagent, was prepared by contacting a 33% solution ofdodecyltrimethylammonium (N,N,N-trimethyl-1-dodecanaminium) chloridewith a hydroxide-for-halide exchange resin (one liter of wet resin with1.4 milliequivalent/ml exchange capacity per 2 l of the solution). Itwill be referred to as 33% DOTMA-OH.

The wet cake of Example 1 (50 g, about 20% solids) was mixed with 500 mlg of DOTMA-OH and heated in the steambox for 4hours. The solid wasisolated by filtration and washed with water. The air dried productshowed X-ray diffraction pattern similar to that of FIG. 2 with a veryintense low angle line. The X-ray diffraction pattern for this swollenmaterial is given in the following Table 21.

                  TABLE 21                                                        ______________________________________                                        2 Theta    d(A)           I/I.sub.o × 100                               ______________________________________                                        1.7        52.0           100                                                 6.15       14.37          25     broad                                        6.31       14.01          6                                                   7.02       12.59          18                                                  7.92       11.16          6                                                   9.39       9.42           11                                                  12.74      6.95           6                                                   14.13      6.27           7      broad                                        15.63      5.67           7                                                   18.88      4.70           11     broad                                        19.95      4.45           20     broad                                        22.34      3.98           17                                                  23.49      3.79           7                                                   24.85      3.58           13                                                  25.81      3.45           28                                                  26.57      3.35           12                                                  27.93      3.19           14                                                  ______________________________________                                    

A portion of the swollen product was mixed with the TMA-silicatesolution described above (Example 3) in the weight ratio 1:10,respectively. After 20 hours reaction in the steambox the solid wasfiltered off, air dried and contacted three times with 1M ammoniumnitrate. The final product, obtained by calcination at 540° C. had apattern essentially as described in Table 4. More particularly, theX-ray diffraction pattern for this pillared, calcined material is givenin the following Table 22.

                  TABLE 22                                                        ______________________________________                                        2 Theta    d(A)           I/I.sub.o × 100                               ______________________________________                                        1.8        49.1           100                                                 7.13       12.40          32                                                  8.00       11.05          13                                                  9.88       8.95           11                                                  12.88      6.87           4                                                   14.32      6.18           15                                                  15.94      5.56           4                                                   18.17      4.88           2                                                   20.30      4.37           8      broad                                        21.57      4.12           6                                                   21.96      4.05           10                                                  22.65      3.93           15                                                  23.75      3.75           10                                                  25.04      3.56           9                                                   26.06      3.42           29                                                  26.86      3.32           9                                                   27.66      3.22           6      broad                                        ______________________________________                                    

EXAMPLE 12

The Alpha values for the products from Examples 3 and 9 were measured tobe 75 and 116, respectively.

The following Table 23 provides common peaks observed in the X-raydiffraction (XRD) patterns for the swollen materials of the foregoingExamples 2, 4, 6, 7, 9, and 11.

                  TABLE 23                                                        ______________________________________                                        2 Theta   d(A)            I/I.sub.o × 100                               ______________________________________                                        1.7       52.0 ± 10.0  100                                                 5.3       16.7 ± 4.0   2-25                                                7.12      12.41 ± 0.25 6-55                                                8.01      11.04 ± 0.22 3-9    (Note 1)                                     9.53      9.28 ± 0.19  2-11   (Note 1)                                     12.79     6.92 ± 0.14  1-6                                                 14.50     6.11 ± 0.24  1-7                                                 15.68     5.65 ± 0.11  1-7    (Note 3)                                     19.82     4.48 ± 0.09  5-22                                                21.94     4.05 ± 0.08  4-7    (Note 2)                                     22.44     3.96 ± 0.08  8-22   (Note 1)                                     23.41     3.80 ± 0.08  2-9                                                 24.93     3.57 ± 0.07  3-19                                                25.92     3.44 ± 0.07  8-59                                                26.57     3.35 ± 0.07  4-16                                                ______________________________________                                         Note 1: Peak is unresolved in the XRD pattern for Example 7.                  Note 2: Peak is unresolved in the XRD pattern for Examples 7 and 11.          Note 3: Peak is not visible in the XRD pattern for Examples 2 and 9.     

The following Table 24 provides common peaks observed in the X-raydiffraction patterns for the pillared, calcined materials of theforegoing Examples 3, 5, 8, 10, and 11.

                  TABLE 24                                                        ______________________________________                                        2 Theta   d(A)            I/I.sub.o × 100                               ______________________________________                                        1.7       52.0 ± 12.0  100                                                 7.14      12.38 ± 0.25 9-55                                                8.08      10.94 ± 0.22 3-19                                                9.82      9.01 ± 0.18  1-11   (Note 1)                                     12.86     6.88 ± 0.14  1-5                                                 14.38     6.16 ± 0.12  4-26                                                15.86     5.59 ± 0.11  1-5                                                 20.09     4.42 ± 0.09  1-9                                                 21.61     4.11 ± 0.08  1-9                                                 22.02     4.04 ± 0.08  2-12                                                22.63     3.93 ± 0.08  3-19                                                23.67     3.76 ± 0.08  2-13                                                25.07     3.55 ± 0.07  2-11                                                26.04     3.42 ± 0.07  8-35                                                26.76     3.33 ± 0.07  2-21                                                ______________________________________                                    

EXAMPLE 13

120 g of the wet Nu-6(1) material (about 24 g solids), described in U.S.Pat. No. 4,397,825, was contacted three times with 1.25 l of 2M HCl for2.5 hr at 90° C. The solid was washed with water until Cl⁻ free and airdried for overnight yielding 25 g of the solid (MCM-39) with an X-raypowder diffraction pattern shown in Table 25.

                  TABLE 25                                                        ______________________________________                                                d(A) I/I.sub.o                                                        ______________________________________                                                9.45 100                                                                      6.93 12                                                                       5.28 23                                                                       4.65 17                                                                       4.55 98                                                                       4.06 56                                                                       3.88 17                                                                       3.70 98                                                                       3.44 14                                                                       3.34 77                                                                       3.29 35                                                                       3.11  8                                                               ______________________________________                                    

A 9 g sample of the solid was calcined at 450° C. for 20 hours. It wasdetermined to have a BET surface area of 49 m² /g and adsorptioncapacity of 2.9, 2.6 and 3.3 w/w % for water, cyclo-hexane and n-hexane,respectively.

EXAMPLE 14

This Example describes the preparation of swollen/pillared MCM-39. 24 gof the solid from Example 13 was mixed with 150 ml of the 29% CTMA-OH.The slurry was gently stirred for overnight at room temperature,filtered, washed with water and air dried for 6 hours. The swollen solidwas contacted with 216 g of tetraethylorthosilicate for 24 hr at80°-115° C. Following filtration it was hydrolyzed with water (75 g ofsolid, 100 ml of water) for 4 hours and filtered again. This afforded 65g of the pillared product, which was found to have, after calcination at450° C. for 12 hours (33 g), the BET surface area of 650 m² /g, andadsorption capacity for water, c-hexane and n-hexane of 25.8, 18.9, and17.6%, respectively. The pillared product had the X-ray diffractionpattern shown in Table 26.

                  TABLE 26                                                        ______________________________________                                                d(A) I/I.sub.o                                                        ______________________________________                                                40.2 100                                                                      6.83 8                                                                        3.41 7                                                                ______________________________________                                    

What is claimed is:
 1. A process for converting an organic compound,said process comprising contacting an organic compound with a catalystunder sufficient conversion conditions, said catalyst comprising apillared, layered crystalline oxide prepared according to a methodwhereby a layered crystalline oxide is prevented from being transformedby calcination into a non-swellable zeolite, said method comprising thesteps of:(i) intercepting said layered crystalline oxide in anintermediate, swellable state; (ii) swelling the swellable, layeredcrystalline oxide of step (i) with a swelling agent under conditionssufficient to, produce a swollen, layered crystalline oxide; (iii)pillaring the swollen, layered crystalline oxide with a pillaring agentunder conditions sufficient to insert interspathic oxide material inbetween the layers of the layered, crystalline oxide; and (iv) calciningthe pillared, layered crystalline oxide under conditions sufficient totransform the intercepted, layered crystalline oxide of step (i), in theabsence of steps (ii) and (iii), into said non-swellable zeolite,wherebya pillared, layered crystalline oxide is formed and the transformationof a layered, crystalline oxide into a non-swellable zeolite isprevented.
 2. A process according to claim 1, wherein said pillared,layered crystalline oxide has an Alpha Value of at least
 10. 3. Aprocess according to claim 1, wherein said pillared, layered crystallineoxide has an Alpha Value of at least
 50. 4. A process according to claim1, wherein said pillared, layered crystalline oxide has pores in thelayers thereof, said pores having pore windows formed by rings of atleast 8 oxygen atoms.
 5. A process according to claim 3, wherein saidpillared, layered crystalline oxide has pores in the layers thereof,said pores having pore windows formed by rings of at least 10 oxygenatoms.
 6. A process according to claim 1, wherein said pillared, layeredcrystalline oxide has pores in the layers thereof with a pore diametergreater than about 5 Angstroms.